EP0874066B1 - Revêtement pour supprimer des dépôts carbonés sur composants de moteur - Google Patents

Revêtement pour supprimer des dépôts carbonés sur composants de moteur Download PDF

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Publication number
EP0874066B1
EP0874066B1 EP98302701A EP98302701A EP0874066B1 EP 0874066 B1 EP0874066 B1 EP 0874066B1 EP 98302701 A EP98302701 A EP 98302701A EP 98302701 A EP98302701 A EP 98302701A EP 0874066 B1 EP0874066 B1 EP 0874066B1
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EP
European Patent Office
Prior art keywords
coating
hydrogenated carbon
amorphous hydrogenated
doped amorphous
engine
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Expired - Lifetime
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EP98302701A
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German (de)
English (en)
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EP0874066A1 (fr
Inventor
Timothy J. Potter
Xia Zhang
William Vassell
Michael R. Rigley
Robert E. Hetrick
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Ford Global Technologies LLC
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Ford Global Technologies LLC
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01L—CYCLICALLY OPERATING VALVES FOR MACHINES OR ENGINES
    • F01L3/00—Lift-valve, i.e. cut-off apparatus with closure members having at least a component of their opening and closing motion perpendicular to the closing faces; Parts or accessories thereof
    • F01L3/02—Selecting particular materials for valve-members or valve-seats; Valve-members or valve-seats composed of two or more materials
    • F01L3/04—Coated valve members or valve-seats
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05C—INDEXING SCHEME RELATING TO MATERIALS, MATERIAL PROPERTIES OR MATERIAL CHARACTERISTICS FOR MACHINES, ENGINES OR PUMPS OTHER THAN NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES
    • F05C2201/00—Metals
    • F05C2201/02—Light metals
    • F05C2201/021—Aluminium
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05C—INDEXING SCHEME RELATING TO MATERIALS, MATERIAL PROPERTIES OR MATERIAL CHARACTERISTICS FOR MACHINES, ENGINES OR PUMPS OTHER THAN NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES
    • F05C2201/00—Metals
    • F05C2201/04—Heavy metals
    • F05C2201/0433—Iron group; Ferrous alloys, e.g. steel
    • F05C2201/0448—Steel

Definitions

  • This invention relates to deposit resistant internal combustion engine components and a method of preventing the formation of carbonaceous deposits on engine components with the use of an amorphous hydrogenated carbon coating thereon.
  • carbonaceous deposits which form on the surfaces of the intake and exhaust valves, the intake port, and the surfaces on the combustion chamber head and the top of the piston, pose a particular problem.
  • Carbonaceous deposits for example on engine intake and exhaust valves, as well as other combustion chamber components, have profound negative effects with respect to startability, cold start emissions and cold engine driveability of an automobile. Reduction of these deposits would help reduce regulated emissions and preserve a cold start fuelling strategy at high mileage.
  • the intake valve deposits act like a sponge to retain fuel injected into the intake port, at cold start, such deposits may prevent efficient evaporation of the fuel and inhibit or negatively impact startability. This may be especially important in terms of regulated hydrocarbon emissions at cold start where one would have to over-fuel to compensate for the deposits to achieve sufficient vapour to start the engine. As the engine warms, but before the exhaust catalyst is fully warmed, the excess fuel absorbed by the carbonaceous deposits may find its way out the exhaust system as unburned hydrocarbons. Over-fuelling at cold start is already required to achieve a prompt start. This over-fuelling is a well-established cause of hydrocarbon emissions during this period. As valve deposits accumulate during engine operation, additional over-fuelling may be required to achieve cold start, with a corresponding increase in emissions. As a result, the reduction of deposits plays an important role in the reduction of regulated emissions, especially hydrocarbon emissions.
  • Another approach for preventing deposits is a chemical method. Under this approach, a coating is supplied by which the precursor molecules for forming a deposit cannot chemically bond to the surface.
  • An example of this approach is a Teflon® coating.
  • Teflon® coatings are unsuited for application on many engine components due to the high temperature and high hardness properties required for use in an internal combustion engine.
  • an object of the present invention is to prevent the formation of carbonaceous deposits on engine components.
  • Another object of the present invention is to provide a coating for engine components which reduces hydrocarbon emissions.
  • Yet another object of the present invention is to provide a coating for engine components which preserves a cold-start fuelling strategy.
  • a method according to claim 1 for providing a deposit resistant coating for an engine component.
  • the invention also discloses an engine component in an internal combustion engine according to claim 8.
  • engine component as used herein is intended to include all components near or within the combustion chamber of an internal combustion engine which have surfaces on which carbonaceous deposits may form.
  • Such engine components include, but are not limited to, the intake manifold, intake port, intake and exhaust valves as well as surfaces within the combustion chamber that are subject to deposition, including but not limited to, the top of the piston, the portion of the engine head that is exposed in the combustion chamber and surfaces of various components that are mounted in the engine head and exposed to the combustion chamber such as spark plugs and fuel injectors in the case of direct injection spark-ignited engines.
  • the present invention serves to provide an amorphous hydrogenated carbon (AHC) coating for engine components which prevents or minimises the accumulation of carbonaceous deposits thereon.
  • AHC amorphous hydrogenated carbon
  • those surfaces which are susceptible or prone to deposit formation are coated with the amorphous hydrogenated carbon coating disclosed in this invention.
  • an intake valve could be coated, on two surfaces, the surface exposed to the intake port, as well as the surface exposed to the combustion chamber to reduce deposits in these regions.
  • the top of the piston and the portion of the engine head that is exposed in the combustion chamber are surfaces susceptible or prone to deposit formation and thus surfaces which could be coated with the AHC film of this invention.
  • the amorphous hydrogenated carbon coating serves to prevent the formation of carbonaceous deposits because the surface of the coating is chemically inert with respect to deposit formation chemistry.
  • the AHC coating of the present invention is sufficiently hard to withstand application inside the combustion chamber.
  • hydrogenated carbon films are devoid of crystallinity, are amorphous in nature and have very smooth surfaces which impart a low coefficient of friction. Hydrogenated carbon films are utilised because of their high hardness and wear resistant properties. Hydrogenated carbon films are believed to consist of isolated sp 2 carbon-carbon bonded clusters. These clusters may be linked by an sp 3 carbon-carbon bond to form a rigid three-dimensional structure. Due to its structure, the film imparts low friction and wear resistance to its underlying substrate. At low relative humidity, hydrogenated carbon films exhibit friction coefficients in the range of 0.05-0.16 under a contact stress ranging from 0.83 to 1.5 GPa at a sliding speed ranging from 0.03 to 1 meter per second.
  • a carbon based film creates a hard coating with a low coefficient of friction.
  • a diamond-like carbon-based film imparts hardness properties, while a graphite or amorphous carbon-based film imparts lubricant properties.
  • the amorphous carbon includes a dopant to alter the process such that the resultant carbon film is sufficiently hard and deposit resistant.
  • the film coating of the present invention which creates a deposit resistant coating, can be selected from the following group of amorphous hydrogenated carbon and doped hydrogenated carbon.
  • the list of possible dopants include, but are not limited to, tantalum, titanium, tungsten, niobium, silicon, boron, nitrogen, oxygen and fluorine.
  • the preferred film coating for engine components is a silicon-doped amorphous hydrogenated carbon film coating.
  • Silicon-doped amorphous hydrogenated carbon is the preferred film coating due to its increased hardness-a characteristic of silicon-carbide.
  • the addition of silicon in the film coating formation process allows carbon to bond with silicon to create a carbon-hydrogen-silicon film coating with sufficient hardness.
  • silicon-doped amorphous hydrogenated carbon film is the preferred film coating, other amorphous hydrogenated carbon film coatings demonstrate resistance to the formation of deposits and may be used as well.
  • the amorphous hydrogenated carbon film is formed from a hydrocarbon source, such as, for example: ethane, ethylene, acetylene, methane, butane, propane, hexane, benzene, toluene, and xylene.
  • a hydrocarbon source such as, for example: ethane, ethylene, acetylene, methane, butane, propane, hexane, benzene, toluene, and xylene.
  • An amorphous hydrogenated carbon film of the present invention preferably has up to 20-60 atomic percent of hydrogen and most preferably between 35 and 50 atomic percent of hydrogen to achieve a low coefficient of friction.
  • the AHC film coating preferably is 200 angstroms to 10 microns in thickness. Most preferably, the AHC coating has a thickness between 2 and 4 microns.
  • AHC Coatings especially on the order of a few micrometers in thickness can substantially reduce component wear as well as reduce friction among rubbing components especially in oil deprived conditions.
  • These AHC films have high hardness and low friction against many technologically important surfaces including steel which serves to increase the wear resistance of the surface. It is further understood that the addition of silicon to the coating serves to reduce compressive stress within the coating which is beneficial for improving adhesion to the substrate.
  • amorphous hydrogenated carbon films of the present invention can be applied by various techniques, including direct current, radio frequency, plasma-assisted chemical vapour deposition, ion beam deposition and arc discharge techniques. While a number of different methods may be used to deposit these coatings onto a substrate, a preferred deposition method, involves a low pressure, plasma enhanced, chemical vapour deposition (PE-CVD) technique.
  • PE-CVD plasma enhanced, chemical vapour deposition
  • this low pressure, in the order of 1-100 milliTorr, technique is carried out in a vacuum chamber 10 where an RF power supply 12 is capacitively coupled with a coupling capacitor 14 to electrodes whose electrical activation sustains the plasma 16 among appropriate precursor gases 18 admitted to the vacuum chamber 10 through a gaseous flow rate controller 20.
  • One electrode is the substrate 22 to be coated, shown schematically as two engine valves, in combination with a support structure 24, while the other electrode in the simplest case, is the grounded wall of the vacuum system which surrounds, but is electrically insulated from the substrate 18.
  • the precursor gases include at least one hydrocarbon species such as methane or other hydrocarbon gases to form the amorphous hydrogenated carbon.
  • Other gaseous constituents can be included in appropriate proportions, for example, gases of silicon compounds can be included to provide a silicon dopant for the AHC film coating.
  • gases of silicon compounds include those of silicon tetrachloride, SiCl 4 , silicon tetrafluoride, SiFl 4 , trichlorosilicon, SiHCl 3 , and tetramethylsilicon, Si-(CH 3 ) 4 .
  • a self bias which acts to beneficially accelerate positive species composed of ionised precursors or gas constituents to the substrate where they react to form the desired coating.
  • Important coating properties such as hardness, coefficient of friction, internal stress (effecting adhesion) and the like are a function of the self bias potential.
  • the self bias which is not strictly a DC potential but has an alternating component at the applied RF frequency, is itself a function of many process parameters including pressure, gas composition, electrode shape, and the like, and is measured approximately during operation by measuring the potential between the substrates and ground.
  • Optimum coating properties such as hardness, wear and coefficient of friction were found for self bias potential in the range from 200 V to 800 Vrms, which corresponds to an average kinetic energy for carbon ions impacting the substrate of between 50 to 200 electron Volts.
  • the PE-CVD technique is particularly advantageous for a number of reasons.
  • a complex surface may be coated without resorting to a rotation of the substrate which is often required for uniform coating when a unidirectional ion beam coating technique is utilised.
  • the spatial requirements for a large vacuum system and mechanical rotational apparatus, for establishing rotation with respect to the beam especially one that is economically desirable for simultaneous coating of a large number of parts, renders beam techniques impractical from a cost view.
  • the PE-CVD approach can be accomplished while expending a small amount of power per unit surface area of substrate at a substrate temperature which may be constrained in the range of 100° C to 200° C.
  • a substrate temperature which may be constrained in the range of 100° C to 200° C.
  • this interlayer is generally achieved by physical vapour deposition (PVD), such as magnetron sputtering of an interlayer of chromium, aluminium, titanium, titanium nitride (TiN), or silicon.
  • PVD physical vapour deposition
  • This added physical vapour deposition step requires additional equipment and processing.
  • this PVD step is a line-of-site process that makes coating parts with complex shapes difficult and even impossible in some cases, and limits the number of parts that can be closely packed and stacked inside the process chamber.
  • a silicon-containing amorphous hydrogenated carbon film is deposited as an interlayer by plasma deposition using tetraethoxysilane [TEOS, (C 2 H 5 O)Si] as a precursor.
  • This interlayer deposition method involves the step of cleaning the parts using chemical cleaning techniques and argon sputtering cleaning in a vacuum chamber.
  • the TEOS is introduced in the process chamber by using a heated low-vapour-pressure liquid delivery system as a precursor gas.
  • a reactive plasma is then generated and the Si-AHC film is then deposited from the ions drawn from the plasma to the parts by the bias potential.
  • the Si-AHC film is then deposited as provided in the aforementioned U.S. patents assigned to the Ford Motor Company and directed to the application of a silicon-containing amorphous hydrogenated carbon film to finish the coating process.
  • the TEOS interlayer deposition method uses the plasma process used for Si-AHC deposition, a conformal coating process. This deposition method simplifies the equipment set up and streamlines the process procedure by not requiring magnetron sputtering and a sample rotation system. Moreover, this interlayer deposition method provides improved production efficiency and reduces the inherent costs by enabling simultaneous coating of multiple parts. As a result, plasma deposition of an interlayer film from tetraethoxysilane (TEOS) precursor improves the adhesion of silicon-containing amorphous hydrogenated carbon coating on steel and other ferrous automotive components.
  • TEOS tetraethoxysilane
  • an interlayer that can be conformally coated by a plasma process which replaces the sputter chromium interlayer, a line-of-site process, that is presently used.
  • a plasma process which replaces the sputter chromium interlayer, a line-of-site process, that is presently used.
  • a steel disk and engine intake valve were coated with 5,000 Angstroms of the Si-AHC film using TEOS as an interlayer, followed by a deposition of the two micrometer Si-AHC coating.
  • the Si-AHC film provided good adhesion of Si-AHC films to steel and silicon substrates and thus evidences the beneficial adhesion characteristics associated with this interlayer deposition method.
  • Raman spectroscopy is useful for identifying the film coating of the present invention.
  • the diamond-like structure creates a characteristic structure as seen by Raman spectroscopy which yields a broad band at around 1550 cm -1 and a shoulder band at around 1400 cm -1 .
  • the AHC coating of this invention can be applied to a variety of substrate materials, including aluminium, magnesium, steel, and other ferrous materials.
  • Figure 2 shows a cross-sectional view of a portion of an internal combustion engine 26.
  • Several components, or surfaces of a given component can benefit from a coating that eliminates or reduces the formation of deposits.
  • the piston head 28, the engine head 30, the exposed surfaces of the intake 32, and exhaust valves respectively constitute components on which such a coating would be beneficial.
  • the surfaces of components mounted on the head which would have an exposure to the combustion chamber such as spark plugs 34 and in some engine designs a fuel injector, constitute additional target components.
  • the build-up of deposits on any of the aforementioned components can result in engine "knock" and correspondingly reduce performance.
  • the operating parameters of the engine may be reduced from those values that yield optimum results without the deposits.
  • the compression ratio may be reduced, which results in a corresponding decrease in the gasoline mileage, assuming all other factors remaining the same.
  • the reduction of the compression ratio reduces the temperature rise of the combustible charge during compression and correspondingly the potential for premature ignition of that charge by deposits of low thermal conductivity whose temperature can rise to a high enough value during compression to cause premature ignition of the charge.
  • FIG 3 also shows an intake or exhaust valve assembly 36 with the stem of the valve 38 in the valve guide 40 and the head 42 of the valve in proximity to the valve seat 44.
  • the valve head 42 could be coated, on both the side exposed to the intake port 46, as well as the side exposed to the combustion chamber 48 which would reduce deposits in these regions which are harmful to different aspects of engine operation as previously discussed.
  • the deposit of the AHC coating on the valve head 42 region which contacts the valve seat 44 on valve closure will eliminate or reduce wear on the valve head in the region of contact.
  • wear is well known and is measured by the tip height, as provided by distance 1 as shown in Figure 3, corresponding to the distance between a fiducial position on the engine and the top, or tip, of the valve stem. Wear in the valve stem 38 or its contacting region on the valve head 42 during engine operation results in an increase in the tip height and degradation of optimum engine performance.
  • valve stem 38 and the region over which the valve stem passes through the valve guide 40 would allow clearance between the guide and the stem to be reduced without increasing overall friction or wear as a result of the low coefficient of friction of the coating. Such a reduction would be desirable to avoid oil leakage through the valve guide into the intake port and subsequently into the combustion chamber where undesirable hydrocarbon emissions may evolve. Accordingly, the AHC coating of the present invention can be applied to different surfaces of an engine component to achieve different beneficial results.
  • a 6-cylinder, four stroke, spark ignited engine manufactured by Ford Motor Company having a total piston displacement of 3.0 litre and a compression ratio of 10 was run for 300 hours in a high speed durability test.
  • the fuel utilised constituted 85% unleaded gasoline and 15% methanol.
  • the fuel contained no special additives for reducing the deposits.
  • the engine was provided with three coated intake and exhaust valves and three uncoated intake and exhaust valves, two valves per cylinder. In a direct comparison of the coated and uncoated valves, the coated valves showed a distinct reduction of the black, gummy carbonaceous deposits.
  • a second engine test was performed with coated intake and exhaust valves on a turbo-charged 2.2 litre, four valve per cylinder, four stroke, spark-ignited engine.
  • the engine was run for 300 hours in a durability cycle using conventional leaded fuel with no special additives to prevent deposits.
  • no deposits were observed on the Si:AHC coated valves after the test.
  • a substantial layer of carbonaceous deposits is generally observed after similar tests with the same engine and similar fuel composition, where the valves are devoid of the Si:AHC coating.
  • engine tests are, of course, the most conclusive evidence of the efficiency of these carbon coatings
  • laboratory tests are supportive, and if correlated with engine tests, can provide quick verification of changes in the coating process which can optimise the coating for reducing deposits, such as operation at a different self bias voltage or changing the precursor gas.
  • One laboratory test that provides such a verification is that of measuring the contact angle which water and/or other organic liquids make with the coated surface in question as process parameters are altered.
  • Figure 4 shows a plot of the contact angle of distilled water droplets on a number of surfaces, including Teflon®, Si:AHC, and the latter surface subjected to immersion in hydrofluoric acid solution (10% by volume), and subsequently heated for 15 minutes to between 100 and 150° C., respectively, in air.
  • Teflon® which is a well-known coating due to its low wetability and low adhesive energy, has a larger contact angle than Si:AHC, but that the contact angle with the latter can be modified by surface treatment in hydrofluoric acid which causes the contact angle to increase.
  • the chemical treatment might be expected to replace the hydrogen and carbon-hydrogen or silicon-hydrogen bonds near the surface of the coating with fluorine.
  • doped amorphous hydrogenated carbon films include tantalum-doped amorphous hydrogenated carbon, titanium-doped amorphous hydrogenated carbon, tungsten-doped amorphous hydrogenated carbon, niobium-doped amorphous hydrogenated carbon, silicon-doped amorphous hydrogenated carbon, boron-doped amorphous hydrogenated carbon, nitrogen-doped amorphous hydrogenated carbon, oxygen-doped amorphous hydrogenated carbon and fluorine-doped amorphous hydrogenated carbon.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
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Claims (8)

  1. Procédé de réalisation d'un revêtement sur un composant de moteur d'un moteur à combustion interne, comprenant :
    la préparation d'au moins une surface du composant de moteur devant être revêtue afin de créer une surface adhérente,
    l'application sur la surface préparée, par dépôt au plasma, d'un film de couche intermédiaire d'un carbone hydrogéné amorphe contenant du silicium en utilisant le tétra-éthoxysilane en tant que précurseur, et
    l'application sur la couche intermédiaire, par dépôt au plasma, d'un revêtement choisi parmi le groupe constitué de carbone hydrogéné amorphe et de carbone hydrogéné amorphe dopé.
  2. Procédé selon la revendication 1, dans lequel l'étape d'application du film de couche intermédiaire comprend :
    la mise en place du composant de moteur dans une chambre à vide,
    l'évacuation du gaz à l'intérieur de ladite chambre à vide,
    l'établissement d'un mélange de gaz réactifs de tétra-éthoxysilane à l'intérieur de ladite chambre à vide en utilisant un système de distribution de liquide à faible tension de vapeur chauffé, et
    l'établissement d'une décharge de plasma à l'intérieur de ladite chambre à vide, de sorte que le composant de moteur soit une électrode dans ladite décharge de plasma et qu'un revêtement soit déposé sur le composant de moteur.
  3. Procédé selon la revendication 2, comprenant une étape supplémentaire consistant à appliquer le revêtement sur le composant ayant le film de couche intermédiaire appliqué sur celui-ci, lequel comprend :
    l'évacuation du gaz à l'intérieur de ladite chambre à vide,
    l'établissement d'un mélange de gaz réactifs à l'intérieur de ladite chambre à vide, dans lequel ledit mélange de gaz réactifs est choisi parmi le groupe constitué de composés gazeux du silicium, de composés gazeux d'hydrocarbures, et de mélanges de ceux-ci, et
    l'établissement d'une décharge de plasma à l'intérieur de ladite chambre à vide, de sorte que le composant de moteur soit une électrode dans ladite décharge de plasma et qu'un revêtement soit déposé sur le composant de moteur.
  4. Procédé selon l'une quelconque des revendications précédentes, dans lequel ladite couche intermédiaire et ledit revêtement sont appliqués à une température inférieure à 200 °C.
  5. Procédé selon l'une quelconque des revendications précédentes, dans lequel ledit revêtement est de 200 angströms à 10 micromètres d'épaisseur.
  6. Procédé selon l'une ou l'autre de la revendication 1 ou de la revendication 2, dans lequel ledit carbone hydrogéné amorphe dopé est choisi parmi le groupe constitué de carbone hydrogéné amorphe dopé au silicium, de carbone hydrogéné amorphe dopé au bore, de carbone hydrogéné amorphe dopé à l'azote, de carbone hydrogéné amorphe dopé à l'oxygène, de carbone hydrogéné amorphe dopé au fluor, de carbone hydrogéné amorphe dopé au niobium, de carbone hydrogéné amorphe dopé au tungstène, de carbone hydrogéné amorphe dopé au titane, et de carbone hydrogéné amorphe dopé au tantale.
  7. Procédé selon l'une quelconque des revendications précédentes, dans lequel ledit revêtement de carbone hydrogéné amorphe est formé à partir d'une source d'hydrocarbure comprenant au moins l'un de ce qui suit : l'éthane, l'éthylène, l'acéthylène, le méthane, le butane, le propane, l'hexane, le benzène, le toluène et le xylène.
  8. Composant de moteur revêtu destiné à un moteur à combustion interne pouvant être obtenu par le procédé de l'une quelconque des revendications précédentes.
EP98302701A 1997-04-21 1998-04-07 Revêtement pour supprimer des dépôts carbonés sur composants de moteur Expired - Lifetime EP0874066B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US08/837,679 US5771873A (en) 1997-04-21 1997-04-21 Carbonaceous deposit-resistant coating for engine components
US837679 2001-04-18

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EP0874066A1 EP0874066A1 (fr) 1998-10-28
EP0874066B1 true EP0874066B1 (fr) 2002-08-21

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US10519854B2 (en) 2015-11-20 2019-12-31 Tenneco Inc. Thermally insulated engine components and method of making using a ceramic coating
US10578050B2 (en) 2015-11-20 2020-03-03 Tenneco Inc. Thermally insulated steel piston crown and method of making using a ceramic coating
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DE19922161A1 (de) * 1998-05-18 1999-12-09 Fraunhofer Ges Forschung Anti-Haft-Beschichtung und Verfahren zu ihrer Herstellung
US6264439B1 (en) * 1998-06-18 2001-07-24 Wilson Greatbatch Ltd. Low power electromagnetic pump
US6802457B1 (en) * 1998-09-21 2004-10-12 Caterpillar Inc Coatings for use in fuel system components
JP2000120869A (ja) * 1998-10-15 2000-04-28 Teikoku Piston Ring Co Ltd 摺動部材及びその製造方法
FR2784695B1 (fr) * 1998-10-20 2001-11-02 Snecma Densification de structures poreuses par infiltration chimique en phase vapeur
US6085714A (en) 1998-12-11 2000-07-11 Hitco Carbon Composites, Inc. Carbon--carbon composite valve for high performance internal combustion engines
US6145763A (en) * 1998-12-30 2000-11-14 Ford Global Technologies, Inc. Carbonaceous deposit-resistant coating for fuel injectors
US6076487A (en) * 1999-02-25 2000-06-20 Go-Tec Internal combustion system using acetylene fuel
EP1114881A4 (fr) * 1999-06-18 2007-05-16 Nissin Electric Co Ltd Film de carbone, procede de formation associe, article recouvert de ce film, et procede de preparation de cet article
US6715693B1 (en) * 2000-02-15 2004-04-06 Caterpillar Inc Thin film coating for fuel injector components
JP2002097914A (ja) * 2000-07-18 2002-04-05 Fuji Oozx Inc チタン合金製エンジンバルブ及びその製造方法
US7537835B2 (en) * 2001-09-27 2009-05-26 Kabushiki Kaisha Toyota Chuo Kenkyusho High friction sliding member
DE10234588A1 (de) * 2002-07-30 2004-02-19 Robert Bosch Gmbh Bauteil eines Verbrennungsmotors mit einem tribologisch beanspruchten Bauelement
US6991219B2 (en) * 2003-01-07 2006-01-31 Ionbond, Llc Article having a hard lubricious coating
EP1462508B1 (fr) 2003-03-26 2009-08-26 Infineum International Limited Utilisation d'une composition comprenant un composé organique de molydène pour la lubrification des films en carbone diamontoide
ES2329573T3 (es) * 2003-03-26 2009-11-27 Infineum International Limited Uso de una composicion que contiene un compuesto de organomolibdeno para la lubricacion de superficies revestidas con carbono semejante a diamante.
JP3891433B2 (ja) * 2003-04-15 2007-03-14 日産自動車株式会社 燃料噴射弁
EP1479946B1 (fr) * 2003-05-23 2012-12-19 Nissan Motor Co., Ltd. Piston pour un moteur à combustion interne
US20050016705A1 (en) * 2003-07-21 2005-01-27 Ford Motor Company Method and arrangement for an indexing table for making spray-formed high complexity articles
CA2442601C (fr) * 2003-09-26 2005-05-24 Westport Research Inc. Systeme d'injection de carburant et methode de fonctionnement pour moteur a carburant gazeux avec preinjection pour allumage par carburant liquide
JP4572688B2 (ja) * 2004-04-27 2010-11-04 株式会社豊田中央研究所 低摩擦摺動部材
US7213586B2 (en) * 2004-08-12 2007-05-08 Borgwarner Inc. Exhaust gas recirculation valve
US20070234720A1 (en) * 2004-08-12 2007-10-11 Borgwarner Inc. Exhaust gas recirculation valve
CN2898333Y (zh) * 2004-09-14 2007-05-09 日产自动车株式会社 内燃机用部件
JP2006112422A (ja) * 2004-09-14 2006-04-27 Nissan Motor Co Ltd 内燃機関用部材及びその製造方法
US7607638B2 (en) 2005-03-08 2009-10-27 Borgwarner Inc. EGR valve having rest position
FR2883925B1 (fr) * 2005-04-05 2007-05-11 Inst Francais Du Petrole Composant balaye par des gaz d'echappement, notamment composant d'un groupe moteur, et procede pour revetir un tel composant
US7790630B2 (en) * 2005-04-12 2010-09-07 Intel Corporation Silicon-doped carbon dielectrics
DE102005019488A1 (de) * 2005-04-27 2006-11-02 Volkswagen Ag Bauteil einer Brennkraftmaschine
US7383806B2 (en) * 2005-05-18 2008-06-10 Caterpillar Inc. Engine with carbon deposit resistant component
US20080271712A1 (en) * 2005-05-18 2008-11-06 Caterpillar Inc. Carbon deposit resistant component
US7422161B2 (en) * 2006-03-30 2008-09-09 Afton Chemical Corporation Treated port fuel injectors
US7607409B2 (en) * 2006-06-22 2009-10-27 Wulff Joseph W Carbide supercell for dry acetylene generation and an internal combustion engine using the same
DE102006029415B4 (de) * 2006-06-27 2023-07-06 Schaeffler Technologies AG & Co. KG Verschleißfeste Beschichtung sowie Herstellverfahren hierfür
US20100326271A1 (en) * 2009-06-25 2010-12-30 Omax Corporation Reciprocating pump and method for making a system with enhanced dynamic seal reliability
US8920213B2 (en) 2010-03-04 2014-12-30 Omax Corporation Abrasive jet systems, including abrasive jet systems utilizing fluid repelling materials, and associated methods
US9163579B2 (en) 2011-11-28 2015-10-20 Federal-Mogul Corporation Piston with anti-carbon deposit coating and method of construction thereof
US9169800B2 (en) * 2011-11-28 2015-10-27 Federal-Mogul Corporation Piston with anti-carbon deposit coating and method of construction thereof
DE102012210796A1 (de) * 2012-06-26 2014-01-02 Schaeffler Technologies AG & Co. KG Verfahren zur Herstellung eines tribologisch belasteten Schichtverbunds, Schichtverbund und Verwendung einer metallorganischen Verbindung zur Herstellung einer Funktionsschicht des Schichtverbunds
US9586306B2 (en) 2012-08-13 2017-03-07 Omax Corporation Method and apparatus for monitoring particle laden pneumatic abrasive flow in an abrasive fluid jet cutting system
BR102012028060A2 (pt) * 2012-10-31 2014-06-24 Mahle Metal Leve Sa Válvula para motores de combustão interna
BR102012031672A2 (pt) * 2012-12-12 2014-09-09 Mahle Metal Leve Sa Válvula para motores de combustão interna
US20160138516A1 (en) * 2013-06-14 2016-05-19 Ks Kolbenschmidt Gmbh Method for producing an oxidation protection layer for a piston for use in internal combustion engines and piston having an oxidation protection layer
FR3022560B1 (fr) * 2014-06-18 2022-02-25 Hydromecanique & Frottement Procede de revetement en carbone dlc du nez des cames d'un arbre a came, arbre a cames ainsi obtenu et installation pour la mise en oeuvre de ce procede
US10626834B2 (en) 2016-05-03 2020-04-21 GM Global Technology Operations LLC Fuel injector for an internal combustion engine
US11577366B2 (en) 2016-12-12 2023-02-14 Omax Corporation Recirculation of wet abrasive material in abrasive waterjet systems and related technology
EP3372658B1 (fr) 2017-03-07 2019-07-03 Infineum International Limited Procédé de lubrification de surfaces
US10808688B1 (en) 2017-07-03 2020-10-20 Omax Corporation High pressure pumps having a check valve keeper and associated systems and methods
US11433637B2 (en) * 2017-08-14 2022-09-06 Nissan Motor Co., Ltd. Heat shield component
US11224987B1 (en) 2018-03-09 2022-01-18 Omax Corporation Abrasive-collecting container of a waterjet system and related technology
CN112203778B (zh) * 2018-06-22 2022-08-30 林德有限责任公司 气缸阀以及用于抑制污染物在气缸和气缸阀中形成的方法
US12064893B2 (en) 2020-03-24 2024-08-20 Hypertherm, Inc. High-pressure seal for a liquid jet cutting system
EP4126452A1 (fr) 2020-03-26 2023-02-08 Hypertherm, Inc. Clapet anti-retour à synchronisation libre
WO2021202390A1 (fr) 2020-03-30 2021-10-07 Hypertherm, Inc. Cylindre pour pompe à jet de liquide à extrémités longitudinales d'interface multifonctionnelles
GB202007640D0 (en) * 2020-05-22 2020-07-08 Castrol Ltd Surface modification of engine components
US11599170B2 (en) * 2020-06-01 2023-03-07 Dell Products L.P. Management of a thermally regulated structure of an information handling system

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5399080A (en) * 1977-02-10 1978-08-30 Ulvac Corp Treating method for inner circumference face of cylinder block
DE3719077A1 (de) * 1987-06-06 1988-12-22 Daimler Benz Ag Beschichtetes ventil fuer verbrennungsmotoren
AU631037B2 (en) * 1989-12-28 1992-11-12 Kabushiki Kaisha Toyota Chuo Kenkyusho Hard and lubricant thin film of amorphous carbon-hydrogen-silicon, iron base metallic material coated therewith, and the process for producing the same
US5309874A (en) * 1993-01-08 1994-05-10 Ford Motor Company Powertrain component with adherent amorphous or nanocrystalline ceramic coating system
US5249554A (en) * 1993-01-08 1993-10-05 Ford Motor Company Powertrain component with adherent film having a graded composition
US5237967A (en) * 1993-01-08 1993-08-24 Ford Motor Company Powertrain component with amorphous hydrogenated carbon film

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008522020A (ja) * 2004-11-25 2008-06-26 株式会社豊田中央研究所 非晶質炭素膜、その形成方法、および非晶質炭素膜を備えた高耐摩耗摺動部材
US10519854B2 (en) 2015-11-20 2019-12-31 Tenneco Inc. Thermally insulated engine components and method of making using a ceramic coating
US10578050B2 (en) 2015-11-20 2020-03-03 Tenneco Inc. Thermally insulated steel piston crown and method of making using a ceramic coating
US11959036B2 (en) 2022-03-22 2024-04-16 General Electric Company Tuning the zeta potential of surfaces for coke mitigation in fuel and oil systems

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US5771873A (en) 1998-06-30

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